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Single-ion magnet behaviour in mononuclear and two-dimensional dicyanamide-containing cobalt(ii) complexes.
2016
Three cobalt(II) complexes of formulae [Co(dca)2(bim)4] (1), [Co(dca)2(bim)2]n (2) and [Co(dca)2(bmim)2]n (3) [dca = dicyanamide, bim = 1-benzylimidazole and bmim = 1-benzyl-2-methylimidazole] were prepared and structurally analyzed by single-crystal X-ray crystallography. Compound 1 is a mononuclear species where the cobalt(II) ion is six-coordinate with four bim molecules in the equatorial positions [Co–Nbim = 2.1546(15) and 2.1489(15) A] and two trans-positioned dca ligands [Co–Ndca = 2.1575(18) A] in the axial sites of a somewhat distorted octahedral surrounding. The structures of 2 and 3 consist of two-dimensional grids of cobalt(II) ions where each metal atom is linked to the other fo…
Hybrid materials containing organometallic cations and 3-D anionic metal dicyanamide networks of type [Cp*2M][M′(dca)3]
2004
A new series of hybrid materials of type [Cp*2M][M′(dca)3] has been prepared by cation templation and structurally characterised (M = Fe(III), Co(III); M′ = Mn(II), Fe(II), Co(II), Ni(II), Cd(II); dca− = N(CN)2−). The crystallographic analysis of [Cp*2Fe][Cd(dca)3] showed that the [Cd(dca)3]− anionic framework is of a symmetrical 3-D α-polonium type, containing octahedral Cd nodes and μ1,5-dca bridging ligands. The [Cp*2Fe]+ cations occupy the cube-like cavities within the framework. The cationic and anionic-framework sublattices remain magnetically independent and display susceptibilities, over the range 300 to 2 K, of a Curie–Weiss nature obtained by adding a S = 1/2 (Cp*2Fe+) or a S = 0 …
Coordination Complexes of a Neutral 1,2,4-Benzotriazinyl Radical Ligand: Synthesis, Molecular and Electronic Structures, andMagnetic Properties
2015
A series of d-block metal complexes of the recently reported coordinating neutral radical ligand 1-phenyl-3-(pyrid-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (1) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, MnII, FeII, CoII, or NiII, with 1,1,1,5,5,5-hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single-crystal X-ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn(1)(hfac)2] and [Fe(1)(hfac)2] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the meta…
Magnetism and Molecular Nonlinear Optical Second-Order Response Meet in a Spin Crossover Complex
2012
International audience; The quadratic hyperpolarizability of two inorganic Schiff base metal complexes which differ from each other by the nature of the central metal ion (FeII or ZnII) is estimated using hyper-Rayleigh light-scattering (HRS) measurements. The investigated FeII microcrystals exhibit a thermal spin-crossover (SCO) from a diamagnetic to a paramagnetic state centered at T1/2 = 233 K that can be reproduced by the HRS signal whose modest intensity is mainly due to their centrosymmetric packing structure. Diamagnetic ZnII microcrystals even lead to much weaker (∼400 times) HRS intensities which are in addition temperature-independent. These observations allow us to ascribe the ch…
Ferromagnetism in [Mn(Cp*) 2 ] + ‐Derived Complexes: the “Miraculous” Stacking in [Mn(Cp*) 2 ][Ni(dmit) 2 ]
2003
The synthesis and characterisation (X-ray structure and magnetism) of metal complexes (Ni, Au) with the [Mn(Cp*)2]+ cation and the dmit2− and dmid2− ligands are reported. [Mn(Cp*)2][Ni(dmit)2] (1) and [Mn(Cp*)2][Au(dmit)2] (2) exhibit the same structural arrangement, built on stacks of [Ni(dmit)2]− pairs separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−A−D+D+A−A−··· motif. On the contrary, the dmid2− derivative [Mn(Cp*)2][Ni(dmid)2]·CH3CN (3) exhibits a totally different structure, built on mixed layers composed of one [Ni(dmid)2]− unit separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−D+D+A−···motif. The layers are separated from each other by perpendicular [Ni(dmid)2]− unit…
Molecular Magnetic Materials from Polyoxometalates
1994
The significance of polyoxometalates in the field of molecular magnetism is discussed. We show that this kind of inorganic complexes provides remarkable examples for the study of the exchange interactions in clusters. On the other hand, we examine the possibility of using these metal oxide anions as magnetic components of molecular materials containing organic tetrathiafulvalenes as electron donor molecules.
First Cobalt(II) Spin Crossover Compound with N4S2-Donorset
2020
Herein we report the synthesis and characterization of a novel bis-tridentate 1,3,4-thiadiazole ligand (L = 2,5-bis[(2-pyridylmethyl)thio]methyl-1,3,4-thiadiazole). Two new mononuclear complexes of the type [MII(L)2](ClO4)2 (with M = FeII (C1) and CoII (C2)) have been synthesized, containing the new ligand (L). In both complexes the metal centers are coordinated by an N4S2-donorset and each of the two ligands is donating to the metal ion with just one of the tridentate pockets. The iron(II) complex (C1) is in the low spin [LS] state below room temperature and shows an increase in the magnetic moment only above 300 K. In contrast, the cobalt(II) complex (C2) shows a gradual spin crossover (S…
Surface Chemistry Controls Magnetism in Cobalt Nanoclusters
2016
Magnetic properties of Co13 and Co55 nanoclusters, passivated by surface ligand shells that exhibit varying electronic interactions with the metal, are studied using density functional theory. The calculations show that the chemical nature of the bond between the ligand and the metal core (X-type or L-type) impacts the total magnetic moment of Co nanoclusters dramatically. Furthermore, the chemical identity of the ligand within each binding motif then provides a fine handle on the exhibited magnetic moment of the cluster. Thus, ligand shell chemistry is predicted to not only stabilize Co nanoclusters, but provide a powerful approach to control their magnetic properties, which combined enabl…
Theory of domain-wall magnetoresistance in metallic antiferromagnets
2020
We develop a theory to compute the domain-wall magnetoresistance (DWMR) in antiferromagnetic (AFM) metals with different spin structures. In the diffusive transport regime, the DWMR can be either {\it negative} or positive depending on the domain-wall orientation and spin structure. In contrast, when the transport is in the ballistic regime, the DWMR is always positive, and the magnitude depends on the width and orientation of the domain wall. Our results pave the way of using electrical measurements for probing the internal spin structure in antiferromagnetic metals.
Gender as a key factor in trace metal and metalloid content of human scalp hair. A multi-site study
2016
This multi-site study discusses the content of metals and metalloids (MM) in scalp hair of children, living in different environmental contexts, with the purpose of verifying if hair level of some MM is distinctively gender-specific. A total of 943 hair samples (537 females and 406 males) from adolescents were analysed for their content of Al, As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, U, V and Zn. Elemental quantification was performed by ICP-MS. The obtained data identified different metal distributions in adolescent girls which exhibited significantly higher hair concentrations of some trace metals, especially Sr, Zn and Ni, than boys. On the base of the median value, hai…